Silver halide photographic material

ABSTRACT

A silver halide photographic material which comprises a compound represented by the following general formulae (Ia) or (Ib): 
     
         R.sup.1 --L.sup.1 --R.sup.2 --L.sup.2 --R.sup.3 --NHNH--G.sup.1 --R.sup.4 
    
      (Ia) 
     
         R.sup.6 --L.sup.3 --R.sup.2 --NHNH--G.sup.1 --R.sup.4      (Ib) 
    
     wherein the terms are as defined in the specification. The photographic material is capable of producing ultrahigh contrast images and is useful in photomechanical processes. An advantage of the material in comparison to prior materials is that can be developed using a developer having a lower pH value.

FIELD OF THE INVENTION

The present invention relates to a silver halide photographic materialand a process for the formation of an ultrahigh contrast negative imageusing the silver halide photographic material. More particularly, thepresent invention relates to a silver halide photographic materialsuitable for use in photomechanical processes.

BACKGROUND OF THE INVENTION

In the field of graphic arts, in order to optimize the reproduction ofcontinuous tone images or line images from a halftone image, imageformation systems which exhibit ultrahigh contrast (particularly gammaof 10 or more) are required.

A known process for the formation of high contrast images comprises theuse of a hydrazine derivative as disclosed in U.S. Pat. Nos. 4,224,401,4,168,977, 4,166,742, 4,311,781, 4,272,606, and 4,211,857. In accordancewith this process, ultrahigh contrast and a high sensitivity can beobtained and the addition of high concentration sulfite to the developeris allowed. Thus, the stability of the developer to air oxidation isdrastically improved as compared with the lithographic developer.

However, the hydrazine compounds used in this type process have beenfound to have some disadvantages. That is, in order to eliminate theadverse effects of hydrazine compounds on other photographiclight-sensitive materials when flowing into the developer, attempts weremade to render the structure of these hydrazine compounds nondiffusive.These nondiffusive hydrazine compounds are disadvantageous in that theymust be used in large amounts to provide sensitization and highcontrast. When used in such large amounts, they tend to deteriorate thephysical strength of the light-sensitive layers thus obtained or theytend to deposit in the coating solution. Furthermore, when alight-sensitive material comprising such a nondiffusible hydrazinecompound is processed with a developer fatigued by the processing of alarge amount of light-sensitive materials, it cannot provide asufficiently high contrast.

Further, since ultrahigh contrast systems employing a hydrazine compoundhave heretofore required a developer having a relatively high pH value,on the order of 11.5 to 11.8, these systems are dangerous to handle andthey have a high BOD or COD in waste disposal. Moreover, since largeamounts of a pH buffer must be used to keep the pH value of thedeveloper constant, the solids content of the developer is increased,making the developer sticky and difficult to wipe after it is scatteredon the photographic material.

Thus, it has been desired to provide a hydrazine compound which canprovide a high contrast in the presence of a developer with a lower pHvalue.

Moreover, light-sensitive materials for contact work commonly used indaylight may be used to make a wide variety of plate-makinglight-sensitive materials. In this field, a high letter image qualityenabling the reproduction of fine Ming type letters has been desired. Tothis end, it has been desired to develop a nucleating agent having ahigher activity. In particular, the nucleating agents currently in usein daylight light-sensitive materials which can be handled in daylightdo not provide sufficiently higher contrast and thus a nucleating agenthaving an even higher activity is desired.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a silverhalide plate-making photographic material which exhibits an excellentrapid-processability and a high processing stability.

It is another object of the present invention to provide a silver halideplate-making photographic material which can be developed in a lower pHrange.

It is further object of the present invention to provide a nucleatingagent having a higher activity.

These and other objects of the present invention will become moreapparent from the following detailed description and examples.

The objects of the present invention are accomplished using a silverhalide photographic material comprising a compound represented by thefollowing general formula (Ia) or (Ib):

    R.sup.1 --L.sup.1 --R.sup.2 --L.sup.3 --R.sup.3 --NHNH--G.sup.1 --R.sup.4 (Ia)

    R.sup.6 --L.sup.3 --R.sup.2 --NHNH--G.sup.1 --R.sup.4      (Ib)

wherein L¹ represents an --SO₂ NR⁵ -- group, an --NR⁵ SO₂ NR⁵ -- group,an --NR⁵ CONR⁵ -- group or a --G² P(O)(G² R⁵)--NR⁵ -- group; L²represents an --SO₂ NR⁵ -- group; L³ represents an --SO₂ NR⁵ -- group,an --NR⁵ SO₂ NR⁵ -- group, a --CONR⁵ -- group, an --NR⁵ CONR⁵ -- groupor a --G² P(O)(G² R⁵)--NR⁵ -- group; G¹ represents a --CO-- group, an--SO₂ -- group, an --SO-- group, a --COCO-- group, a thiocarbonyl group,an iminomethylene group or a --P(O)(G² R⁵)-- group; G² represents asingle bond, an --O-- group or an --NR⁵ -- group; R¹ represents analiphatic or aromatic group containing four or more repeating ethyleneoxide units or an aliphatic or aromatic group containing at least onequaternary ammonium cation; R² and R³ each represents a divalentaliphatic or aromatic group; R⁴ represents a hydrogen atom, an aliphaticgroup, an aromatic group, an alkoxy group, an aryloxy group or an aminogroup; R⁵ represents a hydrogen atom, an aliphatic group or an aromaticgroup; and R⁶ is a group represented by formula (IIb), (IIIb), (IVb) or(Vb):

    R.sup.11 --O--(CH.sub.2 CH.sub.2 O).sub.m --(CH.sub.2).sub.p --(S--(CH.sub.2).sub.r).sub.n --                          (IIb) ##STR1## wherein

R¹¹ represents an aliphatic or aromatic group; and the three R¹¹ 's ingeneral formula (Vb) may be the same or different and they may beconnected to each other to form a ring;

Z¹ represents a group of atoms required to form a nitrogen-containingheterocyclic aromatic group; the suffix m represents an integer from 4to 20;

the suffix n represents 0 or 1 with the proviso that n=1 when L³ is an--SO₂ NR⁵ -- group or a --CONR⁵ -- group;

the suffixes p and r each represents an integer from 1 to 20 and ingeneral formula (IVb), p may be 0;

the suffix q represents 0 or 1;

X⁻ represents a paired anion or a paired anion portion that forms anintramolecular salt. For example, --SO₃ ⁻ portion in Compound A-24 orB-19 exemplified hereinafter corresponds to the paired anion portion.

DETAILED DESCRIPTION OF THE INVENTION

The compounds represented by general formulas (Ia) and (Ib) aredescribed in detail below.

In general formulas (Ia) and (Ib), the aliphatic group represented by R¹is preferably a C₁₋₃₀ aliphatic group, particularly preferably a C₁₋₂₀straight-chain, branched or cyclic alkyl group.

In general formulas (Ia) and (Ib), the aromatic group represented by R:is a monocyclic or bicyclic aryl group or an unsaturated heterocyclicgroup. The unsaturated heterocyclic group may be condensed with arylgroups.

The aliphatic or aromatic group represented by R¹ may be substituted.Examples of suitable substituents for R¹ include an alkyl group, anaralkyl group, an alkenyl group, an alkinyl group, an alkoxy group, anaryl group, a substituted amino group, a ureide group, a urethane group,an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthiogroup, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group,an alkylsulfinyl group, an arylsulfinyl group, a hydroxyl group, ahalogen atom, a cyano group, a sulfo group, an aryloxycarbonyl group, anacyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamidegroup, a sulfonamide group, a carboxyl group, a phosphoric amide group,a diacylamino group, and an imide group. Preferred substituents forR.sup. are an alkyl group (preferably a C₁₋₂₀ alkyl group), an aralkylgroup (preferably C₇₋₃₀ an aralkyl group), an alkoxy group (preferably aC₁₋₂₀ alkoxy group), a substituted amino group (preferably an aminogroup substituted by a C₁₋₂₀ alkyl group), an acylamino group(preferably a C₂₋₃₀ acylamino group), a sulfonamide group (preferably aC₁₋₃₀ sulfonamide group), a ureide group (preferably a C₁₋₃₀ ureidegroup), and a phosphoric amide group (preferably a C₁₋₃₀ phosphoricamide group). These substituent groups may be further substituted byother substituents.

The ethylene oxide group and the quaternary ammonium cation group orgroups contained in R¹ may be included in these substituents.

R¹ is preferably a group that is represented by the following generalformulas (IIa), (IIIa), (IVa) or (Va): ##STR2##

In general formulas (IIa), (IIIa), (IVa) and (Va), R¹¹, Z¹, p, q, r, m,and X. each has the same meaning as defined in general formulas (IIb),(IIIb), (IVb) and (Vb).

In general formulas (IIa), (IIIa), (IVa), (Va), (IIb), (IIIb), (IVb) and(Vb), the aliphatic group represented by R¹¹ is preferably a C₁₋₃₀aliphatic group, particularly preferably a C₁₋₂₀ straight-chain,branched or cyclic alkyl group. The aromatic group represented by R¹¹ isa monocyclic or bicyclic aryl group or an unsaturated heterocyclicgroup. The unsaturated heterocyclic group may be condensed with an arylgroup or groups. The three R¹¹ 's in general (Vb) may be the same ordifferent or they may be connected to each other to form a ring.Examples of nitrogen-containing heterocyclic aromatic groups formed byZ¹ and a nitrogen atom include a pyridine ring, a pyrimidine ring, apyridazine ring, a pyrazine ring, an imidazole ring, an oxazole ring, athiazole ring, benzo-condensed rings thereof, a pteridine ring, and anaphthyridine ring. The suffixes p and r each represents an integer from1 to 20, preferably from 2 to 10. In general formulas (IVa) and (IVb), pmay be 0. R¹¹ and Z¹ may be substituted. Examples of suitablesubstituents for R¹¹ and Z¹ include those set forth as substituents forR¹ in general formulas (Ia) and (Ib).

In general formulas (Ia) and (Ib), the aliphatic group represented by R²and R³ are preferably a C₁₋₃₀ aliphatic group, particularly preferably aC₁₋₂₀ straight-chain, branched or cyclic alkyl group.

In general formulas (Ia) and (Ib), the aromatic groups represented by R²and R³ are a monocyclic or bicyclic aryl group or an unsaturatedheterocyclic group. The unsaturated heterocyclic group may be condensedwith an aryl group or groups.

The groups represented by R² and R³ are preferably an aryl group,particularly preferably an aryl group containing benzene rings.

The aliphatic or aromatic groups represented by R² and R³ may besubstituted. Examples of suitable substituents include those set forthas substituents for R¹.

In general formulas (Ia) and (Ib), the alkyl group represented by R⁴ ispreferably a C₁₋₄ alkyl group, and the aryl group represented by R⁴ ispreferably a monocyclic or bicyclic aryl group (e.g., containing benzenerings).

If G¹ is --CO-- group, then R⁴ is preferably a hydrogen atom, an alkylgroup (e.g., methyl, trifluoromethyl, 3-hydroxypropyl,3-methanesulfonamidepropyl, phenylsulfonylmethyl), an aralkyl group(e.g., o-hydroxybenzyl), or an aryl group (e.g., phenyl,3,5-dichlorophenyl, o-methanesulfonamidephenyl, 4-methanesulfonylphenyl,2-hydroxymethylphenyl). A hydrogen atom is particularly preferred amongthese groups.

R⁴ may be substituted. Examples of suitable substituents for R⁴ includethose set forth as substituents for R¹.

In general formulas (Ia) and (Ib), G¹ is most preferably a --CO-- group.

R⁴ may be a group which causes a cyclization reaction which allows theG¹ --R⁴ portion to be separated from the remainder of the molecule toform a cyclic structure containing --G¹ --R⁴. Examples of such groupsfor R⁴ include those described in JP-A-63-29751 (the term "JP-A" as usedherein means an "unexamined published Japanese patent application").

The group represented by R⁵ is preferably a hydrogen atom or a C₁₋₆alkyl group, particularly preferably a hydrogen atom. If the compoundrepresented by general formulas (Ia) and (Ib) contains two or more R⁵groups or G² groups, they may be the same or different.

In general formulas (Ia) and (Ib), R¹, R², R³, R⁴ or R⁵ may include aballast group or a polymer which is commonly used in immobilephotographic additives such as a coupler. A ballast group is arelatively photographically-inert group containing 8 or more carbonatoms. Suitable ballast groups may be selected from the group consistingof an alkyl group, an alkoxy group, a phenyl group, an alkylphenylgroup, a phenoxy group, and an alkylphenoxy group. Examples of the abovementioned polymer include the polymers described in JP-A-1-100530.

In general formulas (Ia) and (Ib), R¹, R², R³, R⁴ or R⁴ may include agroup which facilitates the adsorption of the compound represented bygeneral formulas (Ia) and (Ib) to the surface of the silver halidegrains incorporated in the photographic material. Examples of suchadsorption groups include the groups described in U.S. Pat. Nos.4,385,108 and 4,459,347, and in JP-A-59-195,233, 59-200,231, 59-201,045,59-201,046, 59-201,047, 59-201,048, 59-201,049, 61-170,733, 61-270,744,62-948, 63-234,244, 63-234,245, and 63-234,246, such as a thioureagroup, a heterocyclic thioamide group, a mercapto heterocyclic group anda triazole group.

Examples of the compounds represented by general formula (Ia) are givenbelow, but the present invention should not be construed as beinglimited thereto. ##STR3##

Examples of the compound represented by the general formula (1b) will begiven below, but the present invention should not be construed as beinglimited thereto. ##STR4##

The hydrazine compounds of the present invention may be synthesizedusing the methods described in JP-A-61-213847, 62-260153, 49-129536,56-153336, 56-153342 and 1-269936, U.S. Pat. Nos. 4,684,604, 3,379,529,3,620,746, 4,377,634, 4,332,878, 4,988,604, and 4,994,365.

A specific example of a suitable synthesis method is set forth below.

SYNTHESIS EXAMPLE: Synthesis of Exemplary Compound A-6

18.4 g of imidazole and then 11.5 g of 2-chloroethylaminemonohydrochloride were added to a mixture of 38.4 g of the startingcompound A shown below and 150 ml of acetonitrile. The mixture was thenstirred at room temperature for 2 hours. The reaction solution waspoured into 500 ml of a 1N aqueous solution of HCl. The reactionsolution was extracted with ethyl acetate, and then dried with magnesiumsulfate anhydride. Ethyl acetate was then distilled off. The residue wasthen subjected to isolation and purification by silica gelchromatography to obtain 29.9 g of Synthetic Intermediate B. ##STR5##

50 ml of a solution of 10.6 g of octyltetraethyleneoxythiol anddimethylformamide was cooled to 15° C. 1.6 g of 50% NaH was added to thesolution, and then heated to room temperature. A solution of 12.4 g ofthe aforesaid Synthetic Intermediate B and dimethylformamide was addeddrop-wise and this reaction solution was stirred at room temperatureovernight. The reaction solution was then poured into a 1N aqueoussolution of HCl including ice. The reaction solution was extracted withethyl acetate, washed with saturated brine, and then dried withmagnesium sulfate anhydride. Ethyl acetate was then distilled off. Theresidue was then subjected to isolation and purification by silica gelchromatography to obtain 7.0 g of the desired compound A-6. The chemicalstructure of the compound was confirmed using NMR spectroscopy and IRspectroscopy.

The hydrazine derivatives of the present invention can be used in theform of solution in an apprepriate water-miscible solvent such as analcohol (e.g., methanol, ethanol, propanol, fluorinated alcohol), aketone (e.g., acetone, methyl ethyl ketone), dimethylformamide,dimethylsulfoxide and methyl cellosolve.

A well known emulsion dispersion method can be used to dissolve thehydrazine compound in an oil such as dibutyl phthalate, tricresylphosphate, glyceryl triacetate or diethyl phthalate or an auxiliarysolvent such as ethyl acetate or cyclohexanone to mechanically preparean emulsion dispersion. Alternatively, a solid dispersion method can beused to disperse a powdered hydrazine derivative of the presentinvention in water using a ball mill, a colloid mill or an ultrasonicapparatus.

Those skilled in the art will know how to make appropriate dispersionwithout undue experimentation.

The amount of the hydrazine derivative to be incorporated in thephototgraphic material of present invention is preferably in the rangeof 1×10⁻⁶ mol to 5×10⁻² mol, particularly 1×10⁻⁵ mol to 2×10⁻² mol permol of silver halide.

In the present invention, if the compound represented by general formula(Ia) or (Ib) is to be incorporated in a photographic light-sensitivematerial, it is preferably incorporated in a silver halide emulsionlayer but may be incorporated in any other light-insensitive hydrophiliccolloidal layer (e.g., a protective layer, an interlayer, a filterlayer, or an antihalation layer). If the compound is to be incorporatedin a silver halide emulsion layer, it may be incorporated at any timebetween the beginning of chemical ripening and before coating,preferably after the completion of chemical ripening but before coating.In particular, the compound is preferably incorporated in a coatingsolution prepared for coating.

The silver halide emulsion to be used in the present invention may haveany suitable composition such as silver chloride, silver bromochloride,silver bromoiodide and silver bromochloroiodide. In the case oflight-sensitive materials for contact work, silver halide having asilver halide content of 60 mol % or more, particularly 75 mol % or moreis preferably used. In particular, silver bromochloride or silverbromochloroiodide containing 0 to 5 % of silver bromide is preferablyused.

In the case of light-sensitive materials for camera work, silver halidehaving a silver bromide content of 70 mol % or more, particularly 90 mol% or more is preferably used. The silver iodide content is preferably inthe range of 10 mol % or less, particularly preferably 0.1 to 5 mol %.

The silver halide grains to be used in the present invention arepreferably finely divided and have a small grain size (e.g., 0.7 μm orless, particularly 0.5 μm or less). The grain size distribution is notcritial but is preferably monodisperse. The term "monodisperse emulsion"as used herein means an emulsion comprising grains at least 95% of whichby weight or number have a grain size falling within ±40% from theaverage grain size.

The silver halide grains in the photographic emulsions may have aregular crystal form such as cubic and octahedral, or an irregularcrystal form such as spherical and tabular, or a combination of thesecrystal forms. In particular, cubic grains are preferably used.

The silver halide grains may have a phase which is uniform throughouteach grain or the grains may have phases that differ from core to shell.Two or more kinds of silver halide emulsions which have been separatelyprepared may be used in admixture.

In the processes for the forming and physically ripening the silverhalide grains, cadmium salts, sulfites, lead salts, thallium salts,rhodium salts, or complex salts thereof, or iridium salts or complexsalts thereof may be used in the system.

Examples of suitable rhodium salts include rhodium monochloride, rhodiumdichloride, rhodium trichloride and ammonium hexachlororhodiumate.Preferably, a water-soluble halogeno complex compound of trivalentrhodium such as hexachlororhodiumic acid (III) or its salts (e.g.,ammonium salt, sodium salt, potassium salt) is used.

The amount of the water-soluble rhodium salt to be added is generally inthe range of 1.0×10⁻⁸ mol to 1.0×10⁻³ mol, preferably 1.0×10⁻⁷ mol to5.0×10⁻⁴ mol per mol of silver halide.

The silver halide emulsion to be used in the present process may or maynot be subjected to chemical sensitization. Processes for chemicalsensitization of the silver halide emulsion include sulfur sensitizationprocess, reduction sensitization processes and noble metal sensitizationprocesses. These chemical sensitization processes can be used singly orin combination.

An example of a noble metal sensitization process is a goldsensitization process. In the gold sensitization process, a goldcompound is used, typically a gold complex salt. Noble metals other thangold, such as platinum, palladium and iridium can be included. Specificexamples of suitable compounds are described in U.S. Pat. No. 2,448,060and British Patent 618,061.

Suitable sulfur sensitizers include sulfur compounds contained ingelatin, and various sulfur compounds such as thiosulfate, thiourea,thiazole and rhodanine, etc.

Suitable reduction sensitizers include stannous salts, amines,formamidinesulfinic acid, silane compounds, etc.

The silver halide emulsion layer to be used in the present invention mayinclude a spectral sensitizing dye. Useful examples of suitable spectralsensitizing dyes include combinations of useful sensitizing dyes andsupersensitizing dyes, and supersensitizing substances as disclosed inResearch Disclosure No. 17643, vol. 176, December 1978, IV-J, page 23.

Gelatin is preferably used as a binder or protective colloid to beincorporated in the hydrophilic emulsion. Other hydrophilic colloids maybe used. Examples of suitable hydrophilic colloids which can be used inthe present invention include proteins such as gelatin derivatives,graft polymers of gelatin with other high molecular compounds, albumine,and casein, saccharide derivatives such as hydroxyethyl cellulose,carboxymethyl cellulose, cellulose ester sulfate, sodium alginate, andstarch derivatives, monopolymers or copolymers such as polyvinylalcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone,polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinyl pyrazole, and other various synthetichydrophilic high molecular compounds.

As gelatin there may be used lime-treated gelatin as well asacid-treated gelatin. Furthermore, hydrolyzates of gelatin and enzymaticdecomposition products of gelatin can be used.

The light-sensitive material of the present invention may includevarious compounds to inhibit fogging during the preparation, storage orphotographic processing of the light-sensitive material or to stabilizephotographic properties. Many compounds are suitable for use as foginhibitors or stabilizers. Examples of suitable fog inhibitors orstabilizers include azoles such as benzothiazolium salts,nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles,mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles,aminotriazoles, benzothiazoles and nitrobenzotriazoles,mercaptopyrimidines, mercaptotriadines, thioketo compounds such asoxazolinethione, azaindenes such as triazaindenes, tetraazaindenes(particularly 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), andpentaazaindenes, hydroquinone and derivatives thereof, disulfides suchas thioctic acid, benzenethiosulfonic acid, benzenesulfinic acid, andbenzenesulfonic amide. Among these compounds, benzotriazoles (e.g.,5-methyl-benzotriazole) and nitroindazoles (e.g., 5-nitroindazole) arepreferred. These compounds may be incorporated in a processing solution.

The light-sensitive material of the present invention may include anorganic desensitizer.

The organic desensitizer preferably contains at least one water-solublegroup and alkali-dissociative group.

Suitable preferred organic desensitizers are exemplified inJP-A-63-64039. If such an organic desensitizer is to be used, it ispreferably incorporated in a silver halide emulsion layer in an amountof from 1.0×10⁻⁸ mol/m² to 1.0×10⁻⁴ mol/m², preferably 1.0×10⁻⁷ mol/m⁷to 1.0×10⁻⁵ mol/m² of the photographic material.

The light-sensitive material of the present invention may include adevelopment accelerator.

Development acceleratos or nucleation infectious developmentaccelerators suitable for use in the present invention include thecompounds disclosed in JP-A-53-77616, 54-37732, 53-137133, 60-140340,and 60-14959 as well as various compounds containing nitrogen or sulfuratoms.

Specific examples of development accelerator compounds are given below.##STR6##

The development accelerator is generally used in an amount of from1.0×10⁻³ g/m² to 0.5 g/m², preferably 5.0×10⁻³ to 0.1 g/m², though theamount will vary depending on the characteristics of the particulardevelopment accelerator. The development accelerator may be incorporatedin a coating solution in the form of solution where the developmentaccelerater is dissloved in an apprepriate solvent such as water, analcohol (e.g., methanol, ethanol), acetone, dimethylformamide or methylcellosolve.

A plurality of such additives may be used in combination.

The emulsion layers of the present invention or other hydrophiliccolloidal layers may include a water-soluble dye as a filter dye or forthe purpose of inhibiting irradiation or other various purposes.Suitable filter dyes include dyes for further lowering photographicsensitivity, preferably an ultraviolet absorbent having a maximumspectral absorption in the inherent sensitivity range of silver halideor a dye having a substantial light absorption in the range of 310 nm to600 nm for improving the safety to safelight when treated as daylightlight-sensitive material.

These dyes may preferably be incorporated in an emulsion layer or in alayer above the silver halide emulsion layer, i.e., a light-insensitivehydrophilic colloidal layer located farther from the support than thesilver halide emulsion layer, together with a mordant.

The amount of such a dye to be incorporated depends on its molarabsorptivity and is normally in the range of 10⁻³ g/m² to 1 g/m²,preferably 10 mg/m² to 500 mg/m².

These dyes may be incorporated in a coating solution in the form ofsolution where the dyes are dissloved in an appropriate solvent such aswater, an alcohol (e.g., methanol, ethanol, propanol), acetone, ormethyl cellosolve or a mixture thereof.

Two or more kinds of these dyes may be used in combination.

Specific examples of these dyes are described in JP-A-63-64039.

In addition, ultraviolet absorbing dyes as disclosed in U.S. Pat. Nos.3,533,794, 3,314,794, 3,352,681, 3,705,805, 3,707,375, 4,045,229,3,700,455, and 3,499,762, JP-A-46-2784, and West German PatentPublication 1,547,863 can also be used.

Other dyes which can be used include pyrazolone oxazole dyes asdisclosed in U.S. Pat. No. 2,274,782, diarylazo dyes as disclosed inU.S. Pat. No. 2,956,879, styryl dyes and butadienyl dyes as disclosed inU.S. Pat. Nos. 3,423,207 and 3,384,487, melocyanine dyes as disclosed inU.S. Pat. No. 2,527,583, melocyanine dyes and oxonol dyes as disclosedin in U.S. Pat. Nos. 3,486,897, 3,652,284, and 3,718,472,enaminohemioxonol dyes as disclosed in U.S. Patent 3,976,661, and dyesas disclosed in British Patents 584,609 and 1,177,429, JP-A-48-85130,49-99620, and 49-114420, and U.S. Pat. Nos. 2,533,472, 3,148,187,3,177,078, 3,247,127, 3,540,887, 3,575,704, and 3,653,905.

The photographic light-sensitive material of the present invention maycontain an inorganic or organic film hardener in a photographic emulsionlayer or other hydrophilic colloidal layer. For example, chromium salts(e.g., chromium alum, chromium acetate), aldehydes (e.g., formaldehyde,glyoxal, glutaraldehyde), N-methylol compounds (e.g., dimethylolurea,methylol dimethyl hydantoin), dioxane derivatives (e.g.,2,3-dihydroxydioxane), activated vinyl compounds (e.g.,1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol),activated halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine),mucohalogenic acids (e.g., mucochloric acid, mucophenoxychloric acid),epoxy compounds (e.g., tetramethylene glycol diglycidyl ether), andisocyanate compounds (e.g., hexamethylene diisocyanate) may be usedsingly or in combination.

Furthermore, high molecular weight film hardeners as disclosed inJP-A-56-66841, British Patent 1,322,971, and U.S. Pat. No. 3,671,256 canbe used.

The photographic emulsion layer or other hydrophilic colloidal layers inthe light-sensitive material prepared according to the present inventionmay include various surfactants to facilitate coating, inhibitelectrification, improve emulsion dispersion and adhesion, and improvingslipperiness and photographic properties (e.g., acceleratingdevelopment, improving contrast, sensitization).

Examples of suitable surfactants include nonionic surfactants such assaponin (steroid series), alkylene oxide derivatives (e.g., polyethyleneglycol, polyethylene glycol/polypropylene glycol condensate,polyethylene glycol alkyl ether or polyethylene glycol alkylaryl ether,polyethylene glycol ester, polyethylene glycol sorbitan ester,polyalkylene glycol alkylamide or amide, and polyethylene oxide additionproducts of silicone), glycidol derivatives (e.g., polyglyceridealkenylsuccinate and alkylphenol polyglyceride), aliphatic esters ofpolyvalent alcohols, or alkylesters of saccharides. Examples of suitableanionic surfactants include anionic surfactants containing acid groupssuch as a carboxyl group, a sulfo group, a phospho group, an estersulfate group or an ester phosphate group (e.g., alkylcarboxylate,alkylsulfonate, alkylbenzenesulfonate, alkylnaphthalenesulfonate,alkylsulfuricester, alkylphosphoric ester, N-acyl-N-alkyltaurine,sulfosuccinic ester, sulfoalkyl polyoxyethylenealkylphenyleher, andpolyoxyethylenealkylphosphoric ester). Other suitable surfactantsinclude amphoteric surfactants such as amino acids, aminoalkylsulfonicacids, aminoalkylsufuric or phosphoric esters, alkylbetaines and amineoxides, and cationic surfactants such as alkylamine salts, aliphatic oraromatic quaternary ammonium salts, heterocyclic quaternary ammoniumsalts (e.g., pyridinium and imidazolium), and aliphatic or heterocyclicgroup-containing phosphonium or sulfonium salts.

Surfactants which can particularly preferably be used in the presentinvention are polyalkylene oxides having a molecular weight of 600 ormore as described in JP-B-58-9412 (the term "JP-B" as used herein meansan "examined Japanese patent publication"). For the purpose ofdimensional stability, a polymer latex such as a polyalkyl acrylate maybe incorporated in the system.

In order to obtain an ultrahigh contrast image using the silver halidephotographic material of the present invention, a stable developer canbe used rather than conventional infectious developers or high alkalidevelopers having a pH value of about 13 such as described in U.S. Pat.No. 2,419,975.

In other words, the silver halide photographic material of the presentinvention can be processed with a developer containing sulfite ions aspreservatives in an amount of 0.15 mol/l or more and having a pH valueof 10.5 to 12.3, particularly 11.0 to 12.0 to obtain a sufficientlyultrahigh negative image.

The developing agents that may be used to develop the photographicmaterial of the present process are not specifically limited. Forexample, dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g.,1-phenyl-3-pyrazolidone and 4,4-dimethyl-1-phenyl-3-pyrazolidone),aminophenols (e.g., N-methyl-p-aminophenol), etc. can be used singly orin combination.

The silver halide photographic material of the present invention isparticularly adapted to be processed with a developer containingdihydroxybenzenes as main developing agents and 3-pyrazolidones oraminophenols as auxiliary developing agents. Preferably, the developercontains dihydroxybenzenes in an amount of 0.05 to 0.5 mol/l and3-pyrazolidones or aminophenols in an amount of 0.06 mol/l or less.

As described in U.S. Pat. No. 4,269,929, amines can be incorporated inthe developer to raise the development speed and shorten the developmenttime.

The developer may further contain a pH buffer such as a sulfite, acarbonate, a borate or phosphate of an alkali metal, a developmentinhibitor such as bromide or iodide, an organic fog inhibitor(particularly nitroindazoles or benzotriazoles), a fog inhibitor, etc.As necessary, water softeners, dissolution aids, color toners,development accelerators, surfactants (particularly the above mentionedpolyalkylene oxides), antifoaming agents, film hardeners, film silverstain inhibitors (e.g., 2-mercaptobenzimidazolesulfonic acids), etc. maybe incorporated in the developer.

As a fixing agent, commonly used compositions are acceptable. Suitablefixing agents include thiosulfates or thiocyanates as well as organicsulfur compounds known to serve as fixing agents. The fixing agent to beused in the present invention may contain a water-soluble aluminumcompound as a film hardener.

The processing temperature in the present invention can be normallyselected from 18° C. to 50° C.

The photographic processing is preferably effected by means of anautomatic processor. In accordance with the present invention, even ifthe total processing time between the entrance and exit of thelight-sensitive material from the automatic processor is set between 90seconds and 120 seconds, a sufficiently ultrahigh contrast negativegradation photograph can be obtained.

The developer to be used in the present invention may include as asilver stain inhibitor a compound as described in JP-A-56-24347. As asolubilization agent to be incorporated in the developer, the compoundsas described in JP-A-61-267759 may be used. Further, as a pH buffer tobe incorporated in the developer, the compounds as described inJP-A-60-93433 and JP-A-62-186259 may be used.

The present invention is further described in the following examples,but the invention should not be construed as being limited thereto.

EXAMPLE 1 1) Preparation of Coated Samples

An aqueous solution of silver nitrate and an aqueous solution of sodiumchloride were simultaneously added to an aqueous solution of gelatinwhich had been kept at a temperature of 40° C. in the presence of (NH₄)₃RhCl₆ in an amount of 5.0×10⁻⁶ mol per mol of silver. Soluble salts wereremoved from the system by a method well known in the art. Gelatin wasthen added to the system. As a stabilizer,2-methyl-4-hydroxy-1,3,3a,7-tetrazindene was added to the system withoutchemical ripening. As a result, a monodisperse emulsion of cubiccrystals having an average grain size of 0.2 μm was obtained.

The emulsion was divided its coating samples and a hydrazine compoundselected from the compounds represented by general formulas (Ia) and(Ib) and set forth in Table 1 below or a comparative compound was addedto each sample in an amount set forth in Table 1. The comparativecompounds have the following structural formulas: ##STR7##

The following nucleation accelerator was added to each emulsion coatingsample in an amount of 15 mg/m² : ##STR8##

A polyethyl acrylate latex in an amount of 30 wt. % based on gelation ascalculated in terms of the solids content and1,3-di-vinylsulfonyl-2-propanol as a film hardener were also added toeach emulsion coating sample.

Each emulsion coating sample was then coated on a polyester support inan amount of 3.8 g/m² on a silver basis and 1.8 g/m² on a gelatin basis.A protective layer was coated a layer comprising gelatin in an amount of1.5 g/m² and polymethyl methacrylate having a grain diameter of 2.5 μmwas then coated on each emulsion layer in an amount of 0.3 g/m².

2) Evaluation of Photographic Properties

The coated samples thus obtained were each imagewise exposed to lightthrough an original as shown in FIG. 1 in JP-A-2-293736 in a daylightprinter P-627FM produced by Dainippon Screen Mfg. Co., Ltd. The exposedsamples were then developed with Developer A whose composition is shownbelow by means of an automatic processor model FG710NH produced by FujiPhoto Film Co., Ltd. at a temperature of 38° C. for 20 seconds, fixedwith a fixing solution GR-F1 produced by Fuji Photo Film Co., Ltd.,rinsed, and then dried.

    ______________________________________                                        Developer A                                                                   ______________________________________                                        Hydroquinone              50.0   g                                            N-methyl-p-aminophenol    0.3                                                 Sodium hydroxide          18.0                                                Potassium hydroxide       55.0                                                5-Sulfosalicylic acid     45.0                                                Potassium sulfite         110.0                                               Disodium ethylenediaminetetraacetate                                                                    1.0                                                 Potassium bromide         10.0                                                5-Methylbenzotriazole     0.4                                                 2-Mercaptobenzimidazole-5-sulfonic acid                                                                 0.3                                                 Sodium 3-(5-mercaptotetrazole)                                                                          0.2                                                 benzenesulfonate                                                              N-n-butyl diethanolmaine  15.0                                                Sodium toluenesulfonate   8.0                                                 Water to make             1      l                                            pH (adjusted with potassium hydroxide)                                                                  11.6                                                ______________________________________                                    

The letter image quality of each sample was evaluated on a scale of 1 to5. On this scale, 5 denotes an excellent letter image quality whichenables reproduction of 30-μm wide letters when exposure is effectedthrough an original as shown in FIG. 1 of JP-A-2-293736 as mentionedabove in such a manner that a 50% dot area in the original reproduced asa 50% dot area on a light-sensitive material for contact work. On theopposite end of the scale, 1 denotes a poor letter image quality whichcan only reproduce letters having a width of 150 μm or more under thesame exposure conditions. Extract letter image qualities 4, 3 and 2denote intermediate extract letter image qualities determined byorganoleptic examination. A letter image quality of 3 or higher equatesto an image quality suitable for practical use.

The Dmax for each sample was also evaluated. Dmax represents the maximumdensity value obtained when the sample was exposed in such a manner thata 50% dot area on the original was reproduced as a 50% dot area on alight-sensitive material for contact work.

Table 1 shows the letter image quality and Dmax for each sample. Theresults in Table 1 show that the samples embodying the present inventionexhibit excellent extract letter image qualities and high Dmax values.

                  TABLE 1                                                         ______________________________________                                                                               Letter                                                      Added amount      image                                  Sample    Compound   (mol/mol Ag)                                                                              Dmax  quality                                ______________________________________                                         1  Com-      Comparative                                                                               1.5 × 10.sup.-3                                                                  3.3   4                                        parison   Compound A                                                       2  Com-      Comparative                                                                               1.5 × 10.sup.-3                                                                  3.2   3                                        parison   Compound B                                                       3  Com-      Comparative                                                                               1.5 × 10.sup.-3                                                                  2.9   3                                        parison   Compound C                                                       4  Invention Compound A-1                                                                              1.5 × 10.sup.-3                                                                  3.5   5                                     5  Invention Compound A-6                                                                              1.5 × 10.sup.-3                                                                  3.7   5                                     6  Invention Compound A-8                                                                              1.5 × 10.sup.-3                                                                  3.8   5                                     7  Invention Compound A-16                                                                             1.5 × 10.sup.-3                                                                  3.4   5                                     8  Invention Compound A-23                                                                             1.5 × 10.sup.-3                                                                  3.4   5                                     9  Com-      Comparative                                                                              0.37 × 10.sup.-3                                                                  2.3   3                                        parison   Compound A                                                      10  Com-      Comparative                                                                              0.75 × 10.sup.-3                                                                  3.1   4                                        parison   Compound A                                                      11  Com-      Comparative                                                                               1.5 × 10.sup.-3                                                                  3.3   4                                        parison   Compound A                                                      12  Com-      Comparative                                                                              0.37 × 10.sup.-3                                                                  2.5   2                                        parison   Compound B                                                      13  Com-      Comparative                                                                              0.75 × 10.sup.-3                                                                  3.1   3                                        parison   Compound B                                                      14  Com-      Comparative                                                                               1.5 × 10.sup.-3                                                                  3.2   3                                        parison   Compound B                                                      15  Com-      Comparative                                                                              0.37 × 10.sup.-3                                                                  1.9   1                                        parison   Compound C                                                      16  Com-      Comparative                                                                              0.75 × 10.sup.-3                                                                  2.5   2                                        parison   Compound C                                                      17  Com-      Comparative                                                                               1.5 × 10.sup.-3                                                                  2.9   3                                        parison   Compound C                                                      18  Com-      Comparative                                                                              0.37 × 10.sup.-3                                                                  1.9   1                                        parison   Compound D                                                      19  Com-      Comparative                                                                              0.75 × 10.sup.-3                                                                  2.4   2                                        parison   Compound D                                                      20  Com-      Comparative                                                                               1.5 × 10.sup.-3                                                                  2.8   3                                        parison   Compound D                                                      21  Com-      Comparative                                                                              0.37 × 10.sup.-3                                                                  2.0   2                                        parison   Compound E                                                      22  Com-      Comparative                                                                              0.75 × 10.sup.-3                                                                  2.9   3                                        parison   Compound E                                                      23  Com-      Comparative                                                                               1.5 × 10.sup.-3                                                                  3.0   3                                        parison   Compound E                                                      24  Invention Compound B-1                                                                             0.20 × 10.sup.-3                                                                  3.1   3                                    25  Invention Compound B-1                                                                             0.37 × 10.sup.-3                                                                  3.3   3                                    26  Invention Compound B-1                                                                             0.75 × 10.sup.-3                                                                  3.6   5                                    27  Invention Compound B-2                                                                             0.20 × 10.sup.-3                                                                  2.6   3                                    28  Invention Compound B-2                                                                             0.37 × 10.sup.-3                                                                  3.1   4                                    29  Invention Compound B-2                                                                             0.75 × 10.sup.-3                                                                  3.9   5                                    30  Invention Compound B-3                                                                             0.20 × 10.sup.-3                                                                  2.8   4                                    31  Invention Compound B-3                                                                             0.37 × 10.sup.-3                                                                  3.6   4                                    32  Invention Compound B-3                                                                             0.75 × 10.sup.-3                                                                  4.1   5                                    33  Invention Compound B-6                                                                             0.20 × 10.sup.-3                                                                  2.9   3                                    34  Invention Compound B-6                                                                             0.37 × 10.sup.-3                                                                  3.6   4                                    35  Invention Compound B-6                                                                             0.75 × 10.sup.-3                                                                  3.8   5                                    36  Invention Compound B-11                                                                            0.37 × 10.sup.-3                                                                  3.0   3                                    37  Invention Compound B-11                                                                            0.75 × 10.sup.-3                                                                  3.5   3                                    38  Invention Compound B-11                                                                             1.5 × 10.sup.-3                                                                  3.6   5                                    39  Invention Compound B-22                                                                            0.37 × 10.sup.-3                                                                  2.9   3                                    40  Invention Compound B-22                                                                            0.75 × 10.sup.-3                                                                  3.5   3                                    41  Invention Compound B-22                                                                             1.5 × 10.sup.-3                                                                  3.5   5                                    ______________________________________                                    

EXAMPLE 2 Preparation of Light-Sensitive Emulsion

An aqueous solution of silver nitrate, an aqueous solution of potassiumiodide and an aqueous solution of potassium bromide were simultaneouslyadded over 60 minutes to an aqueous solution of gelatin which had beenkept at a temperature of 50° C. in the presence of hexachlorinatediridium (III) potassium in an amount of 4×10⁻⁷ mol per mol of silver andammonia while the pAg value of the system was kept at 7.8 to prepare amonodisperse emulsion of cubic grains having an average grain size of0.28 μm and an average silver iodide content of 0.3 mol %. The emulsionwas desalted using a flocculation method. An inert gelatin was thenadded to the emulsion in an amount of 40 g per mol of silver. Theemulsion was kept at a temperature of 50° C. while a KI solution (10⁻³mol/mol Ag) of5,5'-dichloro-9-ethyl-3,3'-bis(3-sulfopropyl)oxacarboncyanine as asensitizing dye was added to the emulsion. The emulsion was allowed tostand for 15 minutes, and then cooled down.

Coating of Light-Sensitive Emulsion Layer

The emulsion was subjected to re-dissolution and divided into coatingsamples. A hydrazine compound represented by general formula (Ia) or(Ib) or a comparative compound was added to each sample at a temperatureof 40° C. and in an amount set forth in Table 2. 5-methylbenzotriazole,2-methyl-4-hydroxy-1,3,3a,7-tetrazaindene, the following compounds (a)and (b), polyethyl acrylate in an amount of 30 wt. % based on gelatin,and the following compound (c) as a gelatin hardener were further addedto each emulsion coating sample. Each emulsion coating sample was thencoated on a 150-μm thick polyethylene terephthalate film having a 0.5-μmthick subbing layer comprising a vinylidene chloride copolymer in anamount of 3.8 g/m² on a silver basis. ##STR9##

Coating of Protective Layer

The emulsion layer of each sample was then coated with gelatin in anamount of 1.5 g/m², polymethyl methacrylate grains having an averagegrain diameter of 2.5 μm in an amount of 0.3 g/m², and finely dividedAgCl grains having an average grain diameter of 0.08 μm in an amountsuch that the amount of silver reached 0.3 g/m² in the presence of thefollowing surfactants. ##STR10##

Evaluation of Properties

Each sample was exposed to tungsten light of 3,200° K. through anoptical wedge and a contact screen (150 L chain dot type, produced byFuji Photo Film Co., Ltd.), developed with the following Developer B ata temperature of 34° C. for 30 seconds, fixed, rinsed, and then dried.

    ______________________________________                                        Developer B                                                                   ______________________________________                                        Hydroquinone              50.0   g                                            N-methyl-p-aminophenol    0.3                                                 Sodium hydroxide          18.0                                                Potassium hydroxide       20.0                                                Potassium sulfite         30.0                                                Disodium ethylenediaminetetraacetate                                                                    1.0                                                 Potassium bromide         10.0                                                5-Methylbenzotriazole     0.4                                                 2-Mercaptobenzimidazole-5-sulfonic acid                                                                 0.3                                                 Sodium 3-(5-mercaptotetrazole)                                                                          0.2                                                 benzenesulfonate                                                              N-n-butyl diethanolmaine  7.0                                                 Sodium toluenesulfonate   8.0                                                 Water to make             1      l                                            pH (adjusted with potassium hydroxide)                                                                  10.7                                                ______________________________________                                    

The halftone dot quality of each sample was evaluated visually andralted on a scale of 1 to 5. On this scale, 5 is excellent and 1 ispoor. Dot qualities of 5 and 4 are practicable for plate-making dotprecursors. A halftone dot quality of 3 is the lowest practicable level.Dot qualities 2 and 1 are impracticable levels.

The Dmax for each sample was also evaluated. Dmax represents the opticaldensity (Dmax) of an area which has been exposed at an exposure (0.5+logE₃) 0.5 higher than the exposure (log E₃) which gives an optical densityof 1.5 on a specimen which has been similarly exposed to light throughan optical wedge and then developed.

The results for each sample are set forth in Table 2. The results inTable 2 show that the samples embodying the present invention had highDmax values and high dot qualities as compared with the comparativesamples.

                  TABLE 2                                                         ______________________________________                                                                              Halftone                                                    Added amount      dot                                     Sample   Compound   (mol/mol Ag)                                                                              Dmax  quality                                 ______________________________________                                        42  Com-     Comparative                                                                              0.8 × 10.sup.-3                                                                   2.2   3                                         parison  Compound A                                                       43  Com-     Comparative                                                                              0.8 × 10.sup.-3                                                                   2.0   2                                         parison  Compound B                                                       44  Com-     Comparative                                                                              0.8 × 10.sup.-3                                                                   1.7   2                                         parison  Compound C                                                       45  Invention                                                                              Compound A-1                                                                             0.8 × 10.sup.-3                                                                   3.7   5                                     46  Invention                                                                              Compound A-6                                                                             0.8 × 10.sup.-3                                                                   3.9   5                                     47  Invention                                                                              Compound A-8                                                                             0.8 × 10.sup.-3                                                                   4.0   5                                     48  Invention                                                                              Compound A-10                                                                            0.8 × 10.sup.-3                                                                   3.1   4                                     49  Invention                                                                              Compound A-11                                                                            0.8 × 10.sup.-3                                                                   3.6   5                                     50  Invention                                                                              Compound A-15                                                                            0.8 × 10.sup.-3                                                                   3.3   4                                     51  Invention                                                                              Compound A-20                                                                            0.8 × 10.sup.-3                                                                   3.4   4                                     52  Com-     Comparative                                                                              0.4 × 10.sup.-3                                                                   1.6   1                                         parison  Compound A                                                       53  Com-     Comparative                                                                              0.8 × 10.sup.-3                                                                   2.2   3                                         parison  Compound A                                                       54  Com-     Comparative                                                                              1.5 × 10.sup.-3                                                                   2.4   3                                         parison  Compound A                                                       55  Com-     Comparative                                                                              0.4 × 10.sup.-3                                                                   1.5   1                                         parison  Compound B                                                       56  Com-     Comparative                                                                              0.8 × 10.sup.-3                                                                   2.0   2                                         parison  Compound B                                                       57  Com-     Comparative                                                                              1.5 × 10.sup.-3                                                                   2.1   2                                         parison  Compound B                                                       58  Com-     Comparative                                                                              0.4 × 10.sup.-3                                                                   1.5   1                                         parison  Compound C                                                       59  Com-     Comparative                                                                              0.8 × 10.sup.-3                                                                   1.7   2                                         parison  Compound C                                                       60  Com-     Comparative                                                                              1.5 × 10.sup.-3                                                                   1.9   2                                         parison  Compound C                                                       61  Com-     Comparative                                                                              0.4 × 10.sup.-3                                                                   1.5   1                                         parison  Compound D                                                       62  Com-     Comparative                                                                              0.8 × 10.sup.-3                                                                   1.7   2                                         parison  Compound D                                                       63  Com-     Comparative                                                                              1.5 × 10.sup.-3                                                                   1.8   2                                         parison  Compound D                                                       64  Com-     Comparative                                                                              0.4 × 10.sup.-3                                                                   1.5   1                                         parison  Compound E                                                       65  Com-     Comparative                                                                              0.8 × 10.sup.-3                                                                   2.1   2                                         parison  Compound E                                                       66  Com-     Comparative                                                                              1.5 × 10.sup.-3                                                                   2.2   3                                         parison  Compound E                                                       67  Invention                                                                              Compound B-1                                                                             0.4 × 10.sup.-3                                                                   3.5   4                                     68  Invention                                                                              Compound B-1                                                                             0.8 × 10.sup.-3                                                                   4.0   5                                     69  Invention                                                                              Compound B-1                                                                             1.5 × 10.sup.-3                                                                   4.2   5                                     70  Invention                                                                              Compound B-2                                                                             0.4 × 10.sup.-3                                                                   3.7   4                                     71  Invention                                                                              Compound B-2                                                                             0.8 × 10.sup.-3                                                                   4.2   5                                     72  Invention                                                                              Compound B-2                                                                             1.5 × 10.sup.-3                                                                   4.4   5                                     73  Invention                                                                              Compound B-3                                                                             0.4 × 10.sup.-3                                                                   4.1   5                                     74  Invention                                                                              Compound B-3                                                                             0.8 × 10.sup.-3                                                                   4.5   5                                     75  Invention                                                                              Compound B-3                                                                             1.5 × 10.sup.-3                                                                   4.6   5                                     76  Invention                                                                              Compound B-6                                                                             0.4 × 10.sup.-3                                                                   3.9   4                                     77  Invention                                                                              Compound B-6                                                                             0.8 × 10.sup.-3                                                                   4.3   5                                     78  Invention                                                                              Compound B-6                                                                             1.5 × 10.sup.-3                                                                   4.5   5                                     79  Invention                                                                              Compound B-11                                                                            0.4 × 10.sup.-3                                                                   3.2   4                                     80  Invention                                                                              Compound B-11                                                                            0.8 × 10.sup.-3                                                                   3.8   4                                     81  Invention                                                                              Compound B-11                                                                            1.5 × 10.sup.-3                                                                   4.2   5                                     82  Invention                                                                              Compound B-22                                                                            0.4 × 10.sup.-3                                                                   3.6   4                                     83  Invention                                                                              Compound B-22                                                                            0.8 × 10.sup.-3                                                                   4.0   4                                     84  Invention                                                                              Compound B-22                                                                            1.5 × 10.sup.-3                                                                   4.5   5                                     ______________________________________                                    

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A silver halide photographic material comprisinga compound represented by the following general formula (Ia) or (Ib):

    R.sup.1 --L.sup.1 --R.sup.2 --L.sup.2 --R.sup.3 --NHNH--G.sup.1 --R.sup.4 (Ia)

    R.sup.6 --L.sup.3 --R.sup.2 --NHNH--G--R.sup.4             (Ib)

wherein L¹ represents an --SO₂ NR⁵ -- group, an --NR⁵ SO₂ NR⁵ -- group,an --NR⁵ CONR⁵ -- group or a --G² P(O)(G² R⁵)--NR⁵ -- group; L²represents an --SO₂ NR⁵ -- group; L³ represents an --SO₂ NR⁵ -- group,an --NR⁵ SO₂ NR⁵ -- group, a --CONR⁵ -- group, an --NR⁵ CONR⁵ -- groupor a --G² P(O)(G² R⁵)--NR⁵ -- group; G¹ represents a --CO-- group, an--SO₂ -- group, an --SO-- group, a --COCO-- group, a thiocarbonyl group,an iminomethylene group or a --P(O)(G² R⁵)-- group; G² represents asingle bond, an --O-- group or an --NR⁵ -- group; R¹ represents analiphatic or aromatic group containing four or more repeating ethyleneoxide units or an aliphatic or aromatic group containing at least onequaternary ammonium cation; R² and R³ each represents a divalentaliphatic or aromatic group; R⁴ represents a hydrogen atom, an aliphaticgroup, an aromatic group, an alkoxy group, an aryloxy group or an aminogroup; R⁵ represents a hydrogen atom, an aliphatic group or an aromaticgroup; and R⁶ is a group represented by formula (IIb), (IIIb), (IVb) or(Vb): ##STR11## wherein R¹¹ represents an aliphatic or aromatic group;and the three R¹¹ 's in general formula (Vb) may be the same ordifferent and they may be connected to each other to form a ring; Z¹represents a group of atoms required to form a nitrogen-containingheterocyclic aromatic group; the suffix m represents an integer from 4to 20; the suffix n represents 0 or 1 with the proviso that n=1 when L³is an --SO₂ NR⁵ -- group or a --CONR⁵ -- group; the suffixes p and reach represents an integer from 1 to 20 and in general formula (IVb), pmay be 0; the suffix q represents 0 or 1; X⁻ represents a paired anionor a paired anion portion that forms an intramolecular salt.
 2. Thesilver halide photographic material of claim 1, wherein R: is selectedfrom the groups represented by general formulas (IIa) to (Va): ##STR12##wherein R¹¹ represents an aliphatic or aromatic group; and the three R¹¹'s in general formula (Va) may be the same or different and they may beconnected to each other to form a ring;Z¹ represents a group of atomsrequired to form a nitrogen-containing heterocyclic aromatic group; thesuffix m represents an integer from 4 to 20; the suffixes p and r eachrepresents an integer from 1 to 20 and in general formula (IVa), p maybe 0; the suffix q represents 0 or 1; and X⁻ represents a paired anionor a paired anion portion that forms an intramolecular salt.
 3. Thesilver halide photographic material of claim 1, wherein G¹ is a --CO--group.
 4. The silver halide photographic material of claim 1, wherein R²and R³ each is an aryl group.
 5. The silver halide photographic materialof claim 1, wherein R⁵ is a hydrogen atom.
 6. The silver halidephotographic material of claim 1, wherein R¹, R², R³ or R⁴ includes aballast group.
 7. The silver halide photographic material of claim 1,wherein R¹, R², R³ or R⁴ includes a group which facilitates theadsorption of the compound of general formula (Ia) or (Ib) to thesurface of the silver halide grains.
 8. The silver halide photographicmaterial of claim 1, wherein the amount of the compound of generalformula (Ia) or (Ib) incorporated in the material is from 1×10⁻⁶ to5×10⁻² mol per mol of silver halide.
 9. The silver halide photographicmaterial of claim 1, wherein the compound of general formula (Ia) or(Ib) is incorporated in a silver halide emulsion layer.
 10. The silverhalide photographic material of claim 1, further comprising adevelopment accelerator.
 11. The silver halide photographic material ofclaim 10, wherein the amount of the development accelerator is from1×10⁻³ to 0.5 grams square meter of photographic material.
 12. Thesilver halide photographic material of claim 1, wherein said compound isrepresented by formula (Ia).
 13. The silver halide photographic materialof claim 1, wherein said compound is represented by formula (Ib).